Alkyl sulfide terminated oligomers

ABSTRACT

1. AN OLIGOMER HAVING THE FORMULA:   R-S-(CH(-R1)-C(-X)(-R2))A-(CH(-R3)-C(-Y)(-R4))B-H   WHEREIN R IS A STRAIGHT OR BRANCHED CHAIN PRIMARY, SECONDARY OR TERTIARY ALKYL GROUP HAVING FROM 5 TO 20 CARBON ATOMS; R1 AND R3 ARE HYDROGEN, METHYL, ETHYL OR -COOH; R2 AND R3 ARE HYDROGEN, METHYL, ETHYL, -COOH OR CH2COOH; Y IS A STRONGLY POLAR GROUP SELECTED FROM THE GROUP CONSISTING OF -COOH, -CONH2, -OCH3, -OCH2H5 AND -CH2OH; X IS A DIFFERENT POLAR GROUP SELECTED FROM THE GROUP CONSISTING OF THE FOREGOING STRONGLY POLAR GROUPS AND -COOC2H4OH, -COOC3H6OH, -CONHCH2OH, -CONHCH3, -CONHC2H5, -CONHC3H7, -COOCH3, -COOC2H5, -CN, -OOCCH3 AND -OOCC2H5; A+B IS FROM 2 TO 50; AND   A/A+B   IS FROM 0.05 TO 0.6; AND WHERE THE OLIGOMER HAS AT LEAST ONE CARBOXYLIC ACID GROUP, THE SAID GROUP MAY BE IN THE FORM OF THE FREE ACID OR THE ALKALINE SALT THEREOF.

nited States Patent 3,839,405 ALKYL SULFIDE TERMINATED OLIGOMERS Leland E. Dannals, Waterbury, Conn., assignor to Uniroyal, Inc., New York, N.Y.

No Drawing. Continuation of abandoned application Ser. No. 547,743, May 5, 1966. This application Feb. 9, 1970, Ser. No. 9,097

Int. Cl. C07c 121/00 US. Cl. 260-4654 10 Claims ABSTRACT OF THE DISCLOSURE An oligomer having the formula:

and OOCC H a+b is from 2 to 50; and

is from 0.05 to 0.6; and, where the oligomer has at least one carboxylic acid group, the said group may be in the form of the free acid or the alkaline salt thereof.

This application is a continuation of US. patent application 547,743, filed May 5, 1966, now abandoned.

This invention relates to oligomers and their method of preparation. More specifically, the invention relates to oligomers having a backbone of carbon atoms and appendant polar groups.

The oligomers of the invention may be used as surface active agents, emulsifiers or thickeners.

Broadly, the oligomers of the invention are alkyl sulfide terminated compounds having a backbone of from 4 to 100 carbon atoms in addition to those of the alkyl sulfide group. Attached to the oligomeric carbon atoms are appendant polar groups. At least one polar group is present for each two carbon atoms in the chain. The oligomers are generally water soluble, either by themselves or as alkaline salts. The method of the invention results in a product having a very narrow molecular weight distribution, e.g., the polydispersity index is always less than 2 and frequently as low as 1.4 to 1.5, as determined by the Gel Permeation Chromatographic technique.

Generically, the oligomers may be represented by the following formula;

lib l a l a 4 r? {at H X a H Y b it being understood that the formula is not intended to depict the actual structure of the final compounds, because the structural units;

units are randomly distributed in the molecule.

In the above generic formula, R is a straight chain primary (normal), branched chain primary, secondary, or tertiary alkyl group having from 5 to 20, preferably 6 to 12 carbon atoms or mixtures thereof; R and R are hydrogen, methyl, ethyl or COOH groups; R and R are hydrogen, methyl, ethyl, COOH or CH COOH groups; Y is the strongly polar groups COOH, CONH OCH OC H CH OH, and

and X is the aforesaid strongly polar group or the less polar groups COOCH H OH, COOC H OH, CONHCH OH, CONHCH CONHC H CONHC H -COOCH COOC H CN,

COOCH2CHCH2.

Moles of polymerized monomer containing Y substituent Moles of reacted RSH a Tota1 moles of polymerized monomer Moles of reacted RSH Moles of polymerized monomer a containing X substituent a+b Total moles of polymerized monomer The degree of polymerization, a+b, is broadly between 2 and 50, preferably between 10 and 30. The mole fraction of the monomer having the X functional group,

may vary from 0 to 1, unless X is a less polar group in which case the mole fraction must be less than 0.6, preferably less than 0.55. The ratio of a a to b may be varied as desired by those skilled in the art, depending, most importantly, on the desired water solubility of the oligomer or its salts. For example, where the less polar group is either the CN or CONHCH OH the mole fraction is most desirably from 0.3 to 0.5. On the other hand, where one of the other less polar groups are present the preferred mole fraction is less than 0.3.

The molecular weight of the oligomers of the invention is less than 5000, preferably less than 2000, but higher than 200.

The oligomers of the invention may be readily converted to water soluble salts by reaction with various oxides, hydroxides, amines, etc. for their surface active properties. While the ammonium, substituted ammonium and alkali metal salts are broadly soluble, the alkaline earth metal and Group III heavy metal salt may also R S (OH: CHCN/n \CHa CRrCooHjbH where R is a primary or secondary alkyl having from 6 to 12 carbon atoms, preferably a normal alkyl group having from 7 to 11 carbon atoms, and, most desirably, 8 or 10 carbon atoms; R is either hydrogen or methyl; a+b, the degree of polymerization, is broadly from 4 to 50, preferably from 12 to 30, and

is to 0.6, most preferably 0.2 to 0.55. For use as an emulsifier this class of oligomers is converted to the water soluble ammonium, lower alkyl and alkanol substituted ammonium, or alkali metal salts.

Another preferred class of oligomers has the formula:

RS(CH2-C RrC O OH) a( CHr-C RzC ONH1 H b where R is a primary or secondary alkyl, preferably a normal alkyl group having from 6 to carbon atoms, and, preferably, from 7 to 12 carbon atoms; R is either hydrogen, methyl or CH COOH; R is hydrogen or methyl; a+b, the degree of polymerization, is broadly from 6 to 50, preferably from 12 to and is .075 to .40 most preferably 0.075 to .30. When a monofunction acid is present the upper portion of the ranges are preferred while for difunctional acid the lower portions are preferred.

Since this class is water soluble it may be used in its acid form or converted into its water soluble salts as described above.

Examples of the compounds of the instant invention are:

TABLEContinued In preparing the compounds of the instant invention an alkyl mercaptan is reacted with one or more alpha, beta double-bonded monomers. As can be seen from the discussion above one monomer unit must contain a strongly polar group. Examples of these monomers are: acrylic acid, methacrylic acid, alpha-ethylacrylic acid, beta-methyl-acrylic acid, alpha-beta dimethylacrylic acid, hexanoic acid, itaconic acid, maleic acid, fumaric acid, acrylamide, methacrylamide, vinyl ethyl ether, vinyl methyl ether, vinyl pyrrolidone, and allyl alcohol.

Where a second monomer is used it may also be selected from the aforesaid group of strongly polar compounds or be a less polar material such as acrylonitrile, or methylacrylonitrile, ethylacrylonitri-le, methyl acrylate, ethyl acrylate, methyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydyroxyethyl methacrylate, hydroxypropyl methacrylate, vinyl acetate, vinyl propionate, N-isopropyl-acrylamide, N-ethyl acrylamide, N-methyl acrylamide, N-methylolacrylamide, glycidyl acrylate, glycidyl methacrylate.

The reaction is performed in an essentially water-free reaction medium, preferably, in a lower alcohol having a boiling point of less than 100 C., e.g., methanol, ethanol and propanol. Other solvents which dissolve the reactants and the catalyst may also be advantageously used.

Generally, the oligomerization temperature is maintained at 20-60 C. Temperature of up to 100 C. may be used. Optimum temperature may readily be determined for each polymerization and depend on the reaction and relative reactivity of the monomers. In order to facilitate the free radical propagation necessary for an effective catalytic reaction an oxygen-free atmosphere is desirable. This may be obtained by bubbling an inert gas such as nitrogen through the reaction system.

The catalyst employed must be a free radical initiator, such as the peroxides and persulfates. These materials are well known in the art. As required, activators may be added as, for example, N,N'-dimethylaniline. Particularly outstanding results are obtained with organic peroxides and hydroperoxides, hydrogen peroxide, diazo such as diazo bis(isobutyronitrile) and water soluble persulfates. Specific examples include ammonium persulfate, the alkali metal and alkaline earth metal persulfates and the alkyl peroxides such as lauroyl peroxide, cyclohexyl peroxide and t-butyl peroxide. Catalytic amounts of initiator are used, i.e., between 0.1 to 6.0 grams per total mole depending on the particular initiator and the monomers system. For example from 0.1 to 0.5 grams of the ammonium persulfate catalyst are employed per gram mole of monomer (calculated as total moles monomers). If the catalyst is lauroyl peroxide the range is .5 to 6.0 g. While lesser amounts can be used, it will decrease the conversion. Greater amounts give no significant advantage.

A convenient method for carrying out the reaction is to dissolve the alkyl mercaptan initially and the monomer or monomers, as the case may be, in the alcoholic solvent. Thereafter, the catalyst, also dissolved in the solvent, is added slowly. Upon completion of the reaction, the reaction roduct, if it is homogeneous, may be treated with L an aqueous base, as for example an alkali metal hydroxide, such as potassium hydroxide, to neutralize the acid present to a pH of from about 6.5 to 8.5. By vacuum stripping the solvent may be separated leaving a water solution of the salt, e.g., the potassium salt, of the oligomers of the instant invention. However, if the reaction product is heterogeneous, as for example some oligomers precipitate out of the alcohol solvent as they are formed, the product may be isolated by filtration, washing and drying. These products may dissolve in water without the use of an alkali metal hydroxide.

EXAMPLE I Low molecular weight polymers (i.e., oligomers) of the invention having the general formula n-alkyl-S- [acrylonitrile] -[acrylic acidJ -H are prepared in metha- Following the procedure outlined above the reaction is initiated at the reaction temperature by introducing a solution of the initiator at a rate of 38 ml./hr. A total of 0.232 gms. ammonium persulfate per mole of monomer (calcd. as moles of acrylonitrile and acrylic acid only) are added. This equals a total of 2.5 g. of ammonium persulfate.

The transparent greenish-yellow reaction mix is determined to be 65.0% solids, as compared to a theoretical solids content of 65.3%, showing an essentially 100% conversion. The viscosity of the mix is about 1000 cp. After evaporation to dryness at 100 C./2 mm. for 30 minutes, a white, friable powder, soluble in methanol, acetone, methyl ethyl ketone and cyclohexanone, remains. By vapor phase osmometry the number average molecular weight is found to be about 1100 as compared to a calculated value of 1146. Analysis shows the reaction product contains 50% acrylic acid, 36.5% acrylonitrile and 13.5% n-octyl mercaptan and is essentially pure. This material upon conversion to the potassium salt is a useful surface active agent.

Run 2n-octyl-S-[acrylonitrileh- [acrylic acid] -H Following the procedure described in Run 1, 115 g. (1.6 moles) acrylic acid, 84.8 g. (1.6 moles) acrylonitrile, 77.87 g. (0.533 moles) n-octyl mercaptan and 16 g. methanol are added to the reaction flask. 147 ml. of an ammonium persulfate solution (0.66 gms. [NH S O /100 ml. methanol) are added during the /2 hours of the reaction. This is equivalent to 0.303 g./rnole of monomer. The solids obtained are 63.3% indicating a conversion of 93.5%.

Additional runs for preparing R-S-(acrylonitrile),,- (acrylic acid) -H, all using the general procedure described above, are shown in the following Table 1;

TABLE 1 [Preparation of R-S-(acrylonitrile) ,(acrylic acid) s-H oligomers] Materials loaded, g.

0.66 g. (NHm z s per 100 ml. methanol Reaction Percent Acrylic Aerylo- Meth- Ml. G./mole Temp, Time, con- Run No. R a-l-b a/a-l-b acid nitnle RSH anol used monomers 0 hours version 3.. N-Octyl 0. 5 144 106 58. 4 147 0. 243 35 5% 97. 0 4. d 14 0.4 172. 8 84. 8 41. 8 14 1 157 0. 086 35 7 97. 4 5. -d 14 O. 5 144 106 41. 8 35 124. 5 0. 205 35 5% 98. 1 6 do 20 0. 5 129. 6 95. 4 26. 3 36 2 71 0. 126 35 8% 98. 5 n-Dodecyl 14 0. 5 144 106 57. 8 20 105 0. 174 30 8 99. 7 20 0. 4 129. 6 63. 6 30. 3 44 0. 097 35 5% 98. 2 20 0. 5 129. 6 95. 4 36. 4 36 78 0. 138 35 5% 98. 9 16 0. 5 144 106 43. 5 41 146 0. 240 35 6 99. 4 0. 5 216 159 34. 8 61. 5 200 0. 220 7% 98. 7 16 0. 25 216 53 43. 5 133 132 0. 218 35 5% 97. 9

1 The initiator solution used in this run was 0.22 g. (NH4)2SzOa/100 m1. methanol. 2 The initiator solution used in this run was 0.64 g. (NH4)2SzOg/100 ml; methanol.

nol using ammonium persulfate as the initiator. The gen- EXAMPLE II eral procedure employed is to add the acrylic acid, acrylo- 55 nitrile, n-alkyl mercaptan and methanol solvent to a reaction flask which is immersed in a water bath and equipped with an additional funnel, a thermometer, an agitator, a water-cooled condenser and a nitrogen inlet. The solution is agitated, the nitrogen flow commences, and the contents of the flask is heated. When reaction temperature, in this example 35 C., is reached, a solution of the initiator in the methanol is introduced at a controlled rate into the flask via the addition funnel. Because the reaction gives off heat, it is necessary to control the water bath in order to maintain a constant oligomerization temperature.

98.6 g. (0.675 moles) n-octyl mercaptan 110.7 g. methanol Using the same reaction flask as described in Example 1, additional low molecular weight compounds are prepared. In these runs the solvent is isopropanol and the initiator lauroyl peroxide.

Run ln-Octyl-S- [acrylonitrile] [acrylic acidh -H The following materials are added to the reaction flask:

907.2 gm. 12.6 moles) acrylic acid 445.2 gm. (8.4 moles) acrylonitrile 153.2 gm. 1.05 moles) n-octyl mercaptan 10.5 gm. '(0.'5 gm./mole of monomers) lauroyl peroxide 420 gm. isopropanol b The flask is heated to 50 C. by means of the water ath.

After 3 hours it is noted that the reaction mix becomes very viscous. At this time :an additional 591 grams of isopropanol are added. After 4.8 hours 204.1 grams (2.835 mols) of acrylic acid and 136.1 grams isopropanol are added. Additional initiator, namely, 5.25 grams (0.25

9 grams per mole of monomer) of lauroyl peroxide are added after /2 hours. At the end of 9 hours the bath is cooled from the reaction temperature to C. It remains at this temperature until the end of the run. After 24 hours the conversion is 94.8%

The reaction product is a transparent yellowish liquid which contains 56.9% solids and has a viscosity of 16,500 centipoises. After drying the reaction product for 30 minutes at 100 C. at 2 mm. pressure, a solid is obtained which was 62.1% acrylic acid, 9.7% n-octylmercaptan and 25.3% acrylonitrile (a total of 97.1% The intrinsic viscosity in isopropanol of this powder is 0.056. This reaction product can be used as an emulsifier by stripping off the solvent from the aqueous neutralized reaction mixture as described for run 1 in Example I. KOH is used for the neutralization.

Run 2--n-Octyl-S-[acrylic acidh -H In a laboratory reactor are placed 72 g. acrylic acid (1 mole), 14.6 g. (0.1 mole) n-octyl mercaptan, 1.5 g. lauroyl peroxide (1.5 g./mole of monomer), and 350 ml. isopropanol. This is heated by a C. water bath. When the temperature of flask reaches 40 C., 7 drops of N,N- dimethyl aniline (DMA) are added. After 25 minutes, the reaction starts and the temperature reaches 48.5 C. at min. then falls to 409 C. at 3 hours. 15 drops of DMA are then added, but no exotherm results. The reaction product is diluted with water and stripped free of isopropanol without neutralization. It is soluble in Water in its acidic form.

In a laboratory reactor are placed 46.3 g. acrylic acid (0.6429 moles), 4.7 g. n-octyl mercaptan (.032 moles), 1.1 g. lauroyl peroxide, (1.7 g./mole of monomers), and 353.7 g. isopropanol. This is heated by means of a Water bath to 399 C. and 11 drops of DMA are then added. The temperature of the reaction rises to 40.8" C. in thirty minutes, is held at this temperature for 45 minutes and falls to 402 C. during the ensuing 75 minutes. At that time, the addition of 1 g. lauroyl peroxide and 10 drops DMA produces a temperature rise to 404 C. The reaction is continued for 3 hours.

The reaction product is diluted With water and stripped without neutralization to remove the isopropanol. It is soluble throughout this process. A 1% solution has the following surface tensions at the indicated K+pHz 33 d./cm. at pH 3.2; 39 d./cm. at pH 9.5.

In a bottle reactor are placed 36 g. acrylic acid (0.5 moles), 26.5 g. acrylonitrile (0.5 moles), 7.3 g. n-octyl mercaptan (0.05 moles), 6 g. lauroyl peroxide (6 g. mole of monomer) and 274 g. isopropanol. The bottle is rotated for 39 hrs. in a C. bath and solids analysis indicates 88% conversion. The reaction product is neutralized with KOH and stripped. A 10% solution has a surface tension of 27.0 d./cm.

Run 5n-O'ctyl-S-[acrylonitrile1-16- [acrylic acid] -H In a laboratory reactor are placed 21.2 g. acrylonitrile (0.4 moles), 43.2 g. acrylic acid (0.6 moles), 3.65 g. noctyl mercaptan (0.025 moles) and 195 g. isopropanol. The reaction mix is heated to 70 C. and 1 g. lauroyl peroxide is added. The temperature rises to 73.4" C. Lauroyl peroxide is added: 1 g. at the end of 43 min. and 1 g. at the end of 103 min. from initial addition of lauryol peroxide. Reaction is stopped at 6 hours. The conversion is 83.5%.

Run 6-n-Dodecyl-S- [acrylic acidJ -I-I In a laboratory reactor are placed 72 g. acrylic acid (1 mole), 20.2 g. n-dodecyl mercaptan (0.1 mole), 1.5 g. lauroyl peroxide, and 275 g. isopropanol. The reaction is heated to 393 C. and 7 drops DMA (N,N-dimethyl aniline) are added. The temperature rises to 46.7 C. in 1 hour. At 75 min., when temperature drops to 439 C., 8 drops DMA are added, which causes the temperature to rise to 454 C. Subsequent additions of 0.5 g. lauroyl peroxide and 5 drops DMA cause no exotherm. The reaction is stopped after 7.5 hours and the conversion is 98%. The reaction product is diluted with Water and stripped free of alcohol.

Run 7n-Dodecyl-S-[acrylic acidh -H This oligomer is prepared as in Run 6, except for use of 10.1 g. n-dodecyl mercaptan (0.05 moles). The reaction product is diluted with water and stripped free of methanol without neutralization.

Run '8n-Dodecyl-S-[acrylonitrileh -[acrylic acidh -H This oligomer is prepared as in Run 4 except for the use of 10.1 g. n-dodecyl mercaptan in place of the octyl mercaptan. 82% conversion is attained. The reaction mix is neutralized with aqueous KOH and stripped.

Run 9n-Octyl-S-[methyl acrylatek-[acrylic acid] -H In a laboratory reactor are placed 54 g. acrylic acid (0.75 moles), 21.5 g. methyl acrylate (0.25 moles) 7.3 g. n-octyl mercaptan (0.05 moles), 1.5 g. lauroyl peroxide, and 275 g. isopropanol. The reaction mix is heated to 39.3" C. with a water bath and 8 drops of D-MA are added. The temperature rises to 47.0 C. in 40 min. and falls to 452 C. in the following 5 min. Thereafter 8 drops DMA are added and the temperature rises to 47.0 C. and then falls again to 40 C. in the following 90 min. The addition of 0.5 g. lauroyl peroxide and 5 drops DMA shows no exotherm. Conversion was 98.7%.

The reaction mix is diluted with water and stripped free of isopropanol. It is insoluble in water on standing and required KOH neutralization to become a homogeneous solution.

Run 10---n-Dodecyl-S- [methyl acrylate] [acrylic acid] 15-H This oligomer is prepared exactly as in Run 9 except for use of 10.1 g. dodecyl mercaptan (0.05 moles) in place of n-octyl mercaptan. Conversion is 99.5%. The reaction product is diluted with water and stripped free of isopropanol and is neutralized with KOH.

Run 11-R-S-[acrylic acid] -[vinyl pyrrolidone] -H This oligomer is prepared in bottle reactors with 83.25 g. vinyl pyrrolidone, 18 g. acrylic acid and 0.05 moles of n-octyl mercaptan (7.3 g.), 6 g. lauroyl peroxide and 269 g. methanol. The reaction is conducted at 50 C. for 64 hours and a one phase reaction product results. The reaction if repeated with n-dodecyl mercaptan (10.1 g.). Solids indicate 88% conversion for the n-octyl type and for the n-dodecyl.

Run 12---R-S-[acrylic acid] [vinyl pyrrolidoneh -H This oligomer is prepared as in the previous run, except the reaction is run only 16 hours. Two phases formed in the bottle and solids indicate conversions of about 80%.

EXAMPLE III Data are presented, in Table 3, on the preparation and properties of materials represented by the formula, R-S-[A],, -[acrylamide] -H, and in Table 4 similar information on R-S-[A] -[methacrylamideh-H, with [A] representing in both cases a polymerizable carboxylic acid.

The preparation of n octyl-S-[itaconic acidh-[acrylamideh -H, is given in detail here. This general procedure is used for the other synthesis described in Tables 3 and 4.

A wide-mouth gallon jar is charged with 474.4 g. acrylamide, 96.5 g. itaconic acid, 54.2 g. n-octyl mercaptan, 18.6 g. lauroyl peroxide, and 2339 ml. isopropanol. The lid of the jar is fitted with an agitator, gas inlet and out let tube through which nitrogen flowed, and a liquid phase thermometer. This ensemble is placed in a 40 C. constant temperature bath. After 45 minutes the reaction mixture is homogeneous and at a temperature of 37.5 C. The subsequent performance is shown in Table 2.

The reaction mixture is vacuum filtered, and the retained precipitate is washed with 2500 m1. of isopropanol at room temperature and dried to content weight by drawing air through it. On drying this material at 105 C. in a vacuum oven, a weight loss of 5.6% occurred. The weight of white free-flowing powder is 580 g. or a 93% yield based on the weight of acrylamide, itaconic acid, and n-octyl mercaptan.

Analysis of this product shows 1.51% sulfur or 6.89% n-octyl mercaptain, 17.16% itaconic acid, and 14.70% nitrogen or 74.55% acrylamide and thus is essentially pure.

To show distribution of molecular size in this product, 54 g. is dissolved in 240 g. water to form a clear solution. 300 ml. isopropanol is added slowly with agitation. This forms a cloudy, but apparently homogeneous system, but on standing overnight separates into two clear layers. The upper layer is much larger. Separation of these layers and evaporation of solvent gives the following results:

These data show a non-uniform distribution of the sulfur. It is assumed here that the mercaptain determines the molecular size and that there is one sulfur per molecule. A fractionation would separate molecules according to size, so that it is expected that less sulfur would be present in the high molecular weight fraction. Distribution of itaconic acid is uniform however.

From the charge, the molecular Weight of the product is calculated as 1684. Assuming one sulfur per molecule, sulfur analysis shows a molecular weight of 2120, which would be expected since low molecular weight species are probably more soluble in isopropanol, and so do not ap pear in the product or are removed by washing. The freezing point depression of an aqueous solution of the product (5 g. in 95 g. water) is A 0.l05 C. If the molar freezing point depression of the water for this polyelectrolyte were the same as 0.02 molar oxalic acid (A 3.40 C.) a molecular Weight of 1704 would be indicated.

The product dissolved readily in water to make a solution which had a viscosity of 2.1 centipoises at room temperature. The surface tension at various concentrations is given in the following tabulation:

Surface tension, d./ cm.

Concentration, percent:

Percent monovalent cations, viz, sodium, potassium and amweight, Masonic monium, and other divalent cations, viz calcium, magat s- Sulfur acid 5 nesium, zinc and barium, were prepared. All these salts Original 54 51 16 dissolve in water sufficiently to form a 10% solution of 321335 2535 4g gg 83 low viscosity and surface tension.

""" Additional runs are summarized on Tables 3 and 4:

TABLE 3, PART I [Preparation and properties of R-S-[A] .-[aery1arnide]b-H oligomers] Number 2 3 4 5 6 7 s 9 10 11 12 13 14 15 1e Itaconic acid Acrylic acid Itaconio acid a-l- 10 2 20 20 20 20 10 15 20 20 40 40 R ata-i-b) 0. 075 0. 05 0. 10 0. 15 0. 20 0. 10 0. 15 0. 1 0.2 0. 075 0. 10 0.05 0. 1O 0. 05 0.1 0.25

eac 1011:

Initial initiator d 1. 2 1. 7 2. 5 1. 4 1.5 1. 5 0. 4 0.75 0.3 1. 5 2. 3 2. 1 1.82 1. 4 1. 5 1. 3 Incremental initiator 0 0 0 0. 7 2. 2 0 0. 4 0 0 1. 5 0 0 0 0. 9 0. 72 2. 6 Initial activator 0.37 0.51 0. 35 0. 4 0.5 0.24 0. 13 0. 23 0.09 0.45 0.68 0. 62 0.55 0.40 0.50 0. 38 Incremental activator 0 0 0. 41 1.2 0.75 0. 24 0.13 0 0.05 0. 15 0.34 0 O 0. 46 0.24 0. Isopropanol 350 350 350 350 438 350 500 450 400 400 350 350 350 476 350 400 Time, min..- 190 175 170 200 285 135 355 155 145 128 270 150 Yield, percent- 83 98 Product analysi Total 10% aqueous solution:

Viscosity, cp

Surface tension, d./cm

See footnotes at end of Table 3, Part II.

TABLE 3, PART II [Preparation and properties of R-S-[AL,-[acrylamide] -H oligomers] Number 18 19 20 21 22 23 24 25 26 27 Composition:

..... n-Dodecyl n-Octyl h Acrylic acid Maleic acid Methacrylic Fumaric Acrylic acid 40 15 15 2 20 20 20 0. 20 0. 0. 0. 075 0. 15 0. 10 0. 0. 10 0. 20 0. Reaction:

Initial initiator d 0.75 1. 2 1. 2 1. 39 1. 32 0. 6 1. 5 1. 5 0. 75 0. 75 Incremental initiator d 0. 0 0 0 2. 64 1. 2 1. 5 0 0. 38 0. 38 Initial activator 0. 12 0. 3 0. 3 0. 41 0. 40 0. 21 0. 4A 0. 51 0 12 0. 12 Incremental activator 0. 28 0 0 0 1. 00 0.53 0. 88 0 O. 25 0. 25 Isopropanol 1 450 516 576 538 493 450 450 349 450 450 Time, min 255 119 114 155 183 215 180 190 210 Yield, percent 84 92 94 69 82 87 94 89 89 Product analysis, percent:

RSH

Acrylnmidn A Total. 10% aqueous solution:

Viscosity, cp

Surface tension, d./cm

d Initiator, lauroyl peroxide as g./mole of monomers. The R was n-octyl/n-dodecyl in mole ratio of 9/1. Activator, N,N-dimethyl aniline as g./mole of monomers. h The R was n-octyl/n-dodecyl in mole ratlo of 975/25. 1 Isopropanol: ml./mole acrylamide.

EXAMPLE IV TABLE 4 The data of this example show, in Table 5, the prepara- [Preparation and propertiesofR-S-[A] -[methacrylarnideh-H tion and properties of materials represented by the for 10% aqueous solution viscosity, cp

The preparation of n-dodecyl-S-[acrylamide] -H is given in detail, this procedure being used for all syntheses described in Table 5.

The jar reactor is loaded With 80.2 g. acrylamide, 1.4 g. lauroyl peroxide, 565 ml. isopropanol, and 15.2 g. primary dodecyl mercaptan. Nitrogen is passed through the vapor phase of the reactor While the contents are agitated. The reactor is in a 40 C. thermostated bath. After 25 minutes 0.39 g. N,N-dimethyl aniline (DMA) is added through the reflux condenser. Three minutes thereafter the reaction materials turn cloudy and their temperature increases, reaching 45 C. in 18 minutes and then falling to the bath temperature in 103 minutes after the addition of the DMA. The reaction mixture is filtered immediately 5 using a vacuum system. The precipitate is washed with 500 ml. of isopropanol and dried by drawing an air stream through it overnight.

1 Acrylic acid.

,Itaconic mm The free-flowing white precipitate is then dried for 3 'Ihese runs are made in bottl r a t s a hours in a vacuum oven at 1l0112 C. The Weight of 50 the product indicates a yield of 83% based on the amount of acrylamide plus mercaptan.

TABLE 5 [Preparation and properties of R-S-[acry1amide]a-H oligomcrs] Number 1 2 3 4 5 6 Composition:

R n-CoHra 11-CmH21 l'l-CioHzr n-CrzHgs n-CuHzs n-CmHaa a 15 15 40 5 15 15 Reaction conditions, 40 0.:

Lauroylperoxide g/ 01 0.7 0. 7 1 2 l. 2 l 2 0.7 1.0 0 0 0 0 l. 0

0.2 0 15 0 3 0.33 0.35 0 l9 Incremental 0 0 0 0 0 Isopropanol, g./n1ole acrylamide. 300 300 490 500 500 300 Reaction time, minutes 8 76 100 81 103 72 Yield, percent 94 88 34 83 96 Product analysis, percent:

RSH 26. 4 Acrylamirle 73. 5

Total. 99. 9

10% aqueous solution:

Viscosity, cp 3. 4 1.7

Surface tension, d./cm 49 40 1 5 EXAMPLE v This example demonstrates the preparation and properties of N-dodecyl-S-[methacrylamidel -H.

In a bottle reactor is placed 42.5 g. methacrylamide, 1.2 g. lauryl peroxide, 0.3 g. N,N-dirnethyl aniline, 2.50 ml. isopropanol and 6.73 g. primary dodecyl mercaptan. The bottle is flushed with nitrogen, capped, and rotates overnight in a 50 C. bath. The bottle is cooled, opened and the contents are filtered. The precipitate is washed with 250 ml. of isopropanol and then dried first in an air stream and then in a vacuum oven for 3 hours. A yield of 70% is obtained. A aqueous solution of this material has a surface tension of 41.8 d./cm. and a viscosity of 3.0 centipoises. Analysis of the product shows 10.3% n-dodecyl mercaptan and 86.8% acrylamide.

EXAMPLE VI The preparation and properties of n-dodecyl-S-[ethylacrylatejl -[acrylamide] -H type materials are presented here.

A reactor is run for 75 minutes at 40 C. containing 33.7 g. acrylamide, 2.5 g. ethyl acrylate, 2.53 g. normal dodecyl mercaptan, 1 g. lauroyl peroxide. 0.25 g. N,N- dimethyl aniline, and 250 ml. ethanol. The dry precipitate from this reaction indicates 95% yield and as a 10% aqueous solution shows 40.5 d./cm. surface tension and 6.0 centipoises viscosity.

a Run 2. -O.15, a+b 40 A reactor is run for 75 minutes at 40 C. containing 30.2 g. acrylamide, 7.51 g. ethyl acrylate, 2.53 g. ndodecyl mercaptan, 1 g. lauroyl peroxide, 0.25 g. N,N- dimethyl aniline and 250 ml. ethanol. The dried precipitate indicates 95% conversion.

EXAMPLE VII This example demonstrates the preparation and properties of n-dodecyl-S- [vinyl pyrrolidoneh- [acrylamide] -H.

A jar reactor is run for 75 minutes at 40 C. containing 32 g. acrylamide, 5.55 g. vinyl pyrrolidone, 2.53 g. normal dodecyl mercaptan, 1 g. lauroyl peroxide, 0.25 g. N,N- dimethyl aniline and 250 ml. ethanol. The yield is 94%. The product, as a 10% aqueous solution, shows 37.2 d./ cm. surface tension and 5.8 centipoises viscosity.

EXAMPLE VIII The preparation of n-octyl-S-[N-isopropyl acrylamide]; [acrylamideh -H is described here. The following ingredients are stirred under nitrogen for 65 minutes at 40 (3.; 54 g. acrylamide, 21.5 g. N-isopropyl acrylamide, 6.94 g. n-octyl mercaptan, 2.3 g. lauroyl peroxide, 0.64 g. N,N- dimethyl aniline and 421 ml. isopropanol. This reaction mixture does not pass through filter paper readily and the product is isolated by evaporation of the isopropanol. The tan powder resulting is soluble in water.

EXAMPLE IX 1 6 EXAMPLE X This example describes the preparation of n-dodecyl-S- [hydro-xyethyl methacrylate] [acrylamide] -H.

A reactor containing 39.05 g. acrylamide, 12.6 g. hydroxyethyl methacrylate, 3.27 g. n-dodecyl mercaptan, 0.8 g. lauroyl peroxide, and 500 ml. isopropanol, is heated in a 40 C. water bath and 0.028 g. N,N-dimethyl aniline added. The reaction is run 205 minutes and during this time, 1 g. lauroyl peroxide and 0.7 g. N,N-dimethyl aniline is added. The dried precipitate from this reaction is soluble in water. The yield is 99%.

EXAMPLE XI In this example, the preparation of n-dodecyl-S- [vinyl acetate] -[acrylamideh-H type materials is described.

a Run 1. 0.2, a+b 40 In a reactor are placed 58.4 g. acrylamide, 17.7 g. vinyl acetate, 5.2 g. n-dodecyl mercaptan, 1.2 g. lauroyl peroxide, and 500 ml. isopropanol. The contents are heated to 40 C. and 0.34 g. N,N-dimethyl aniline DMA) added. At 25 minutes 0.17 g. DMA is added. After 65 minutes the reaction mixture is filtered and the retained precipitate washed with 500 ml. isopropanol before drying. The yield is 75%.

This differed from Run 1 in the amount of acrylamide (43.8 g.), amount of vinyl acetate (35.4 g.), amount of incremental DMA (0.7 g.), use of 2.4 g. incremental lauroyl peroxide and reaction time of minutes. The yield is 72%.

EXAMPLE XII The preparation and properties of n-dodecyl-S-[acrylonitrile] -[acrylamide] -I-I is described in this example.

Heated to 40 are 57.4 g. acrylamide, 10.7 g. acrylonitrile, 5.1 g. n-dodecyl mercaptan, 1.2 g. lauroyl peroxide, and 500 ml. isopropanol. Then, 0.34 g. N,N-dimethyl aniline are added. The reaction is run minutes and during this time 1.2 g. lauroyl peroxide and 0.68 g. DMA are added. The dried product represents 79% yield and, as a 10% aqueous solution, has 3 centipoises viscosity and 38 d./ cm. surface tension.

EXAMPLE XIII Materials of the n-dodecyl-S-[methylol acrylamide]; [acryIamideJ -H type are described in this example.

a Run 1. 0.167, a+b15 A reactor containing 71 g. acrylamide, 20.2 g. methylol acrylamide, 16.2 g. n-dodecyl mercaptan, 1.2 g. lauroyl peroxide, 0.3 g. N,N-dimethyl aniline and 470 ml. isopropanol is held at 40 C. for 70 minutes. The product is removed by filtration and, when dry, indicates 90% yield. The product is not completely soluble in water as a 10% solution.

In a reactor are placed 71 g. acrylamide, 18.1 g. methylol acrylamide, 6.1 g. n-dodecyl mercaptan, 1.2 g. lauroyl peroxide, 0.3 g. N,N-dimethyl aniline and 485 ml. isopropanol. The reaction mixture is heated to 40 C. and maintained at that temperature for 60 minutes. The dried precipitate, which indicates an 87% yield, is dissolved in water to make a. 10% solution.

EXAMPLE XIV The data of this example show, in Table 6, the preparation and properties of materials represented by the formula R-S- [glycidyl methacrylate],,-[acryIamideL -H.

The syntheses and behavior of a specific product are given in detail.

Run 1: n-Dodecyl-S-[glycidyl methacrylateh- [acrylamideh -H ondary or tertiary alkyl group having from to 20 carbon atoms; R; and R are hydrogen, methyl, ethyl or -CQOH; R and R are hydrogen, methyl, ethyl, -COOH or CH COOH; Y is a strongly polar group selected from the group consisting of -COOH,

5 C c A reaction vessel in a 38.2 C. thermostatted bath, dff ONHZ OCH3 OC2H5 and HLOH; a 1 erent polar group selected from the group conslstmg there is agitated, under nitrogen, 71 g. acrylamide, 35.5 of foregoin strongl mu 8 and g. glycidyl methacrylate, 16.8 g. normal dodecyl mercapg y P g I P tan, 3 g. lauroyl peroxide, 0.75 g. N,N-dimethyl aniline l0 2 4 a a CH2OH, and 463 ml. isopropanol. The reaction temperature rises CONHCH CONHC c to 40.9 C. after 107 minutes and then starts to fall. ONHCsH', Thereafter, 1 g. lauroyl peroxide and 0.25 g. N,N-di- Q s a s N, s d methyl aniline are added, but the temperature continues Q c 1, is f 2 to and to fall. At 225 minutes, the mixture is filtered and the collected precipitate dried in an air stream. This is a white a free-flowing powder. The yield is 81% based on weight a+b of acry1am1de g1ycld1 methacrylate and n'dodecyl is from 0.05 to 0.6; and, where the oligomer has at least captan. Analysis of this product showed 10.4% n-dodecyl one carboxylic acid group, the Said group may be in the mercapfan, acrylamlde! and 274% glycldyl with form of the free acid or the alkaline salt thereof. acrylate for a t tal of 9 2. The oligomer of claim 1 wherein R is primary alkyl- This product dissolves in water to make a 10% soluhaving 6 to 2 carbon atoms; R1, R3 and R4 are b tion having a viscosity of 4 centipoises. On standing over- X is a group; Y is a COOH group; a+b night at room temperature a precipitate forms. When the is f 4 to 0; and fresh solution is evaporated on a steam cone, the solid does not dissolve in, but is swollen by water. Thus this i polyepoxide is apparently self cross-linking.

Table 6 summarizes the above and other runs: is from 0.2 to 0.6.

TABLE 6 [Preparation and properties of R-S-[glyeidyl methacrylate]s-[acrylamideh-H oligomers] Number 1 2 3 4 5 6 Composition:

R n-C12 25 -CsHu n-CuHas n-CrzHas n-CmHn ni2 2i a+b 15 40 20 2o 40 40 al(a+b) 0. 20 0. 20 0. 08 0. 17 0. 20 0. 20 Reaction conditions (Ca. 40 0.):

Lauroyl peroxide, g./mole, monomers:

Initi 2.4 1.26 2.4 2.0 1. 52 2.2 Incremental 0. 8 1. 52 0 0 1. 52 65 N,N-dimethyl aniline, g./mole, monomers:

Initial 0. 6 0. 0. e 0. 5 o. 42 o. 61 Incremental 0. 2 1. 75 0 O 1. 26 O. 61 Isopropanol, ml./mole acrylamide 463 656 470 392 631 g 678 Time, minute 225 115 90 169 120 135 Yield, percent. 8 78 75 87 91 91 Product analysis, percent:

RSH 10.4 Acrylnmidn 60.9 Glycidyl methacrylate 27v 4 8. 9

Total 98.7

Properties:

1 g. product solube in 9 g. H20 Yes Yes Yes Yes Yes Yes Product insolubilized when dried at 100 C Yes Yes Yes Yes Yes Yes EXAMPLE XV In this example, the preparation and properties of ndodecyl-S-[glycidyl acrylateh-[acrylamide] -H are described.

44.2 g. acrylamide, 14.1 g. glycidyl acrylate, 3.7 g. ndodecyl mercaptan, 1.2 g. lauroyl peroxide, 0.4 g. N,N- dimethyl aniline, and 370 ml. isopropanol are agitated under nitrogen in a vessel which is in a C. bath. The temperature of the reaction rises to 44.9 C. after 20 minutes then falls despite additional lauroyl peroxide (1.2 g.) and N,N-dimethyl aniline (0.8 g.). After 67 minutes the product is removed by filtration and dried in an air stream. The yield is 95% based on monomers and mercaptan. The product shows 20.6% glycidyl acrylate.

The free-flowing white powder dissolved in water to make a 10% solution. The product became insoluble after heating the solution to dryness on a stream bath.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. An oligomer having the formula:

wherein R is a straight or branched chain primary, sec- 4. The oligomer of claim 2 wherein R is straight chain primary octyl; a+b is 16; and

L a+b 5. The oligomer of claim 2 wherein R is straight chain primary decyl; a+b is 16; and

.l. a+b

6. The oligomer of claim 2 wherein R is primary dodecyl; a+b is 16; and

19 7. The oligomer of claim 1 wherein R is a primary alkyl group having from 7 to 12 carbon atoms; R R and R are hydrogen; R is hydrogen or CH COOH; X is --COOH; Y is -CONH a+b is from 6 to 50; and

is from 0.075 to 0.15.

9. The oligomer of claim 7 wherein R is n-octyl; R is --CI-I ;COOH; a+b is 20; and

a+b is 0.1.

10. The oligomer of claim 7 wherein R is primary octyl; R is hydrogen; a+b is 20; and

No references cited.

DONALD G. DAUS, Primary Examiner I. TOVAR, Assistant Examiner US. Cl. X.R.

260-29.6, 29.7, 78.5, 80.7, 80.8, 80.81, 82.1, 82.7, 84.3, 85.5, 85.7, 86.1, 86.7, 88.1, 88.7, 89.5, 93.5, 326.22, 326.45, 348 A, 34 R, 429.1, 429.2, 429.9, 465.5 R, 465.6, 481 R, 501.1, 501.11, 501.12, 501.17, 501.21, 543 B, 535 R, 537 S, 540, 541, 561 S, 614, 615 R, 615 P, 632, 635 R mg UNITED STATES PATENT OFFICE Page 1 2 CERTIFICATE OF CORRECTION Patent NO- 3, 39: 5 Dated October Inventor(s) Leland Dannals It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 6: "CHQCOOH" should read -0 COOH line 17 (first formula) COOCH2HLLOH shoul read -cooc HLLOH line 23 isecond formula) -OOCH2H5 should read -OOCC2H5 H H Column A, lane 5. R S (CH CR COOH)a CR CONH 7-g-H should read ----R-S- CH -CR COOH CH -CR CONH H 2 l a 2 2 2 b Column 5, Formula 17 (within the left pair of brackets) (IJH -CH should read CH --CH N N I IE (II-O C-O H ----CH2 CH ---CH Column 5, Formula 2 (within the left pair of brackets) CH should read CH I 3 1 3 CH -C CH-C 2 2 .I

COOCH CH CO COOCH CH Column 7, line 58: "additional" shalld read --addition-- Po-ww UNITED STATES PATENT OFFICE Page 2 of 2 5 CERTIFICATE OF CORRECTION Patent No. 3, 39A 5 Dated October l, 197

Inventor) Leland E. Dannals It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 8, line 3: "38" should read --39---; line 74: "mols" should read -moles--.

Column 9, line 59:

"Run 5--n-Octyl-S-[acrylonitrile]-l6-[acr;ylic acid] H" should read --Run 5--n-Octyl-S-[acrylonitrile] 6-[acrylic acid] -H Column 10 line 1 L "methanol" should read -isopropanol-; line 52: '11?" should read --is--;

line 65: "R-S-[A] [acrylamide] -H" should read R-S-[A] -[acryl;amide] -H Column 13, Table 4, in line "Yield, percent", in column "29": "63" should read --36--.

Column 15, line 3: "N-dodecyl" should read --n-dodecyl--; line 5: "lauryl" should read -'elauroyl.

Columns l'f lg, Table 6, in line "R", in column "6" n-C I-I r should read n-C H in line "Lauroyl peroxide, g./mole, monomers: Incremental", in column "6": "65" should read -l.65--.

Column 18, line A: CHECOOH should read CH2COOH line 69: "6.05" should read --o.5--. line '75: "0,05" should read --O.5-.

Signed and sealed this 13th day of May 1975.

(SEAL) Attest:

c. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks 

1. AN OLIGOMER HAVING THE FORMULA: 